Research Article

Received: 8 July 2013 Revised: 6 September 2013 Accepted article published: 7 October 2013 Published online in Wiley Online Library:

(wileyonlinelibrary.com) DOI 10.1002/pi.4628

Using aluminium triate as a co-catalyst for the polymerization of o-phenylenediamine and its derivatives
Ismael Amer, Desmond A Young and Hermanus CM Vosloo
Abstract
Aromatic diamine monomers, including o-phenylenediamine (oPD), 4-methyl-o-phenylenediamine (4Me-oPD), 4,5-dimethylo-phenylenediamine (dMe-oPD) and 4-(tert-butyl)-o-phenylenediamine (tBu-oPD), were polymerized by chemical oxidation using ammonium persulfate as an oxidant. Aluminium triate (Al(OTf)3 ) was also used for the rst time as a co-catalyst under various reaction conditions for the polymerization of oPD derivatives. The polymerization yield was improved when Al(OTf)3 was introduced to the polymerization reaction for most polymers. The solubility of poly(4-methyl-o-phenylenediamine) (P(4Me-oPD)), poly(4,5-dimethyl-o-phenylenediamine) (P(dMe-oPD)) and poly(4-(tert-butyl)-o-phenylenediamine) (P(tBu-oPD)) polymers was improved compared with the poly(o-phenylenediamine) (P(oPD)) polymers in most common solvents. The homopolymers obtained were characterized by Fourier transform IR spectroscopy, UVvisible spectroscopy, 1 H and 13 C NMR, wide-angle X-ray diffraction, DSC and TGA. The results showed that the yield, solubility and structure of the polymers are signicantly dependent on the polymerization conditions. DSC measurements indicated that the polymers exhibited melting and crystallization transitions. The polymers also showed good thermal stability and decompose above 400 C in nitrogen. c 2013 Society of Chemical Industry Keywords: aluminium triate; FTIR; o-phenylenediamine; oxidative polymerization; NMR; TGA

INTRODUCTION
Polyphenylenediamines are conductive polymers which have attracted much scientic and technological attention in recent years due to their easy preparation and signicant performance in electronic, electrical, thermal, adsorption of heavy metal ion and optical applications.1 15 All three isomers of phenylenediamine can be considered as derivatives of the parent aniline, containing an additional amino group in its ortho-, para- and meta-positions.16 20 The oxidative polymer of o-phenylenediamine (oPD) has displayed various characteristics of molecular structure and properties compared with the extensively studied polyaniline.2 A number of studies have reported that the poly(o-phenylenediamine) (P(oPD)) polymer has signicant multifunctions, such as variable electroactivity,21 distinctive electrochromism,22,23 good permselectivity24 and multiple conductivity.25 Furthermore, P(oPD) polymer has shown considerable applications in the elds of electrochromic lms,22,23 enzyme immobilization,26,27 biosensors,28 electrical and electronic materials,25 anticorrosion coatings for metals29 and immunosorbent assays.30 It was reported that there are two major possibilities regarding the molecular structure of P(oPD) polymer.31 33 A structure having 1,4-substituted benzenoid and quinonoid units was suggested for the polymer obtained by electrochemical polymerization.23 In contrast, a partly phenazine-like structure was proposed for the polymer obtained by chemical oxidative polymerization.34 36 P(oPD) polymer prepared by chemical oxidative polymerization showed unsatisfactory solubility in most of the common organic solvents, despite its relatively high yield,37 and the solubility
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depended on solvent composition and on the oxidant that was used for polymerization.38,39 Therefore, it is challenging to design structures with the purpose of increasing the solubility and fusibility, thus improving the processability of P(oPD) polymer. However, to improve the solubility of P(oPD) polymer but simultaneously maintain the partial phenazine structure and original functionalities and provide additional novel interesting performance, various aromatic amines such as aniline, xylidine, pyrimidylamine and o-phenetidine have been utilized as comonomers by oxidative copolymerization and modied copolymers have been obtained.35 37,40 Copolymerization leads to increased solubility but unfortunately the improvement in the solubility of the copolymers is not very satisfactory and the polymerization yield is still low. Fortunately, it is known that longer side substituents in the polymer chain can lead to greater distortions of the chains and can decrease the interchain van der Waals forces and hydrogen bonding interactions between the polymer chains owing to steric hindrance, which is suitable for improvement of the solubility. Moreover, side groups in the polymer chains display more solvation sites, which also increase the solubility.20

Correspondence to: Ismael Amer, Research Focus Area for Chemical Resource Beneciation: Catalysis and Synthesis Research Group, North-West University, Private Bag X6001, Potchefstroom 2520, South Africa. E-mail: ismaelamer77@yahoo.co.za Research Focus Area for Chemical Resource Beneciation: Catalysis and Synthesis Research Group, North-West University, Private Bag X6001, Potchefstroom, 2520, South Africa

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www.soci.org Metal triates have received signicant interest for their role as Lewis acids in a number of reactions.41 44 Water-tolerant metal triates are especially attractive from both an economical and environmental perspective as they can easily be recycled.45 Thus, aluminium triate (Al(OTf)3 ) is a reusable catalyst which tolerates water effectively and is stable in aqueous medium.46 Al(OTf)3 has not been explored as extensively as other metal triates, e.g. the rare earth metal triates in particular, despite it being comparatively more affordable.46,47 Al(OTf)3 was used in our study as cocatalyst to polymerize different phenylenediamines instead of protic acids which are normally used for polymerizations.48,49 Al(OTf)3 showed an improvement in the yield and had different effects on the molecular weight of phenylenediamine polymers compared with polymerization reactions in which protic acids were used.48 The purpose of this work was to synthesize soluble substituted P(oPD) polymers by chemical oxidative polymerization. The effects of oxidants, polymerization temperature and time, and acidic medium on the polymerization yield, structure, solubility and thermal properties of the P(oPD) polymers were systematically investigated.

I Amer, DA Young, HCM Vosloo 500 and 4000 cm 1 , the resolution used was 2 cm 1 and the results were based on an average of 40 scans. 1 H and 13 C NMR spectra were recorded at room temperature on a Bruker Avance 600 MHz NMR spectrometer. Samples (2030 mg) for NMR analyses were dissolved in deuterated dimethyl sulfoxide (DMSO-d6 ). UVvisible spectra of the polymers at a concentration of 10 mg L 1 in DMSO were recorded on a Varian Cary 50 Conc UVvisible spectrophotometer in a wavelength range 2001000 nm with a scanning rate of 480 nm min 1 , using 1.0 cm quartz cuvette cells. Wide-angle X-ray diffraction (WAXD) analysis was performed on a Bruker AXS D8 Advance diffractometer at room temperature with ltered Cu K radiation. All samples were scanned at 2 angles ranging from 0 to 80 with a sampling width of 0.02 , where 2 is the diffraction angle. DSC analysis was performed on a TA Instruments Q100 DSC. All measurements were conducted in crimped aluminium pans under a nitrogen atmosphere, at a purge gas ow rate of 50 mL min1 . Three cycles were performed for each sample. First the samples were heated from 25 to 450 C at a rate of 10 C min1 . Samples were then cooled from 450 to 25 C. Finally, the samples were heated for a second time at a rate of 10 C min1 to 450 C. TGA was performed on a TA Instruments TGA Q100 with a resolution of 0.1 mg, in a nitrogen atmosphere. Approximately 510 mg of each sample was heated from 20 to 800 C at a rate of 10 C min1 .

EXPERIMENTAL
Materials The oPD, 4-methyl-o-phenylenediamine (4Me-oPD), 4,5dimethyl-o-phenylenediamine (dMe-oPD), 4-(tert-butyl)-ophenylenediamine (tBu-oPD), Al(OTf)3 and all the solvents and reagents were obtained from Aldrich or Fluka (Johannesburg, South Africa) and were used as received. General polymerization procedure The oxidative polymerization was generally accomplished according to reference 50. A typical procedure for the preparation of polymers was as follows. Phenylenediamine monomer (1.7 g) (oPD, 4Me-oPD, dMe-oPD or tBu-oPD) was added to water or hydrochloric acid (150 mL) in a 500-mL round-bottomed ask in an oil bath at specic temperatures (Table 1) and was magnetically stirred. In a separate ask, the oxidant solution consisting of ammonium persulfate ((NH4 )2 S2 O8 ) (4.0 g) and/or Al(OTf)3 (1.0 g) in 20 mL of water was prepared. The polymerization reaction was started by steadily adding the oxidant solution dropwise into the monomer solution at a rate of approximately one drop every 3 s over a period of 30 min. The dropwise addition of oxidant solution produced polymers with a relatively high molecular weight and narrow molecular weight distribution, as the highly exothermic nature of the polymerization reaction could then be effectively controlled. Immediately after the addition of the rst few drops of oxidant, the color of the reaction solution changed according to the color of the polymer powders, shown in Table 1. The reaction mixture was vigorously stirred for at least 24 h. Thereafter, the reaction mixture was ltered and washed several times with an excess of distilled water to remove the oxidant and oligomers. Finally, the resulting powder products were left to dry in ambient air for 1 week. Characterization Fourier-transform infrared spectroscopy (FTIR) was used to characterize the molecular structure of the aromatic diamine polymers. Infrared spectra of the samples were recorded on a Bruker Vertex 80 FTIR spectrometer at room temperature using attenuated total reectance. The analysis was performed between

RESULTS AND DISCUSSION

Figure 1 shows the structures of the oPD, 4Me-oPD, dMe-oPD and tBu-oPD monomers that were used in this study. Moreover, Table 1 summarizes the synthesis conditions, yield and colors of the P(oPD), poly(4-methyl-o-phenylenediamine) (P(4Me-oPD)), poly(4,5-dimethyl-o-phenylenediamine) (P(dMe-oPD)) and poly(4(tert-butyl)-o-phenylenediamine) (P(tBu-oPD)) polymers produced in our experiments. Polymerization yield Generally, it was found that the oxidative polymerization yield (gram of oxidation products per gram of phenylenediamine monomers) of P(oPD) polymers was higher than that of P(4MeoPD), P(dMe-oPD) and P(tBu-oPD) polymers (except for the P(oPD) polymer prepared using HCl solution as solvent (run 2 in Table 1)). The lower yields of P(4Me-oPD), P(dMe-oPD) and P(tBuoPD) polymers compared with P(oPD) polymers is probably due to steric hindrance of the methyl and tert-butyl groups on the aromatic rings.20 Moreover, P(4Me-oPD) polymers showed a higher yield than P(tBu-oPD) polymers which could be due to the higher steric hindrance of tert-butyl groups in P(tBu-oPD) polymers compared with the methyl groups in P(4Me-oPD) polymers. In addition, the polymerization yields of P(oPD), P(4Me-oPD), P(dMeoPD) and P(tBu-oPD) polymers were higher when water was used as solvent and ammonium persulfate as oxidant (runs 1, 4, 7 and 10 respectively in Table 1) compared with those obtained in aqueous HCl solution (runs 2, 5, 8 and 11 respectively in Table 1). These results agreed with the results in our previous study for oPD, pPD, 4,4-diaminodiphenylenemethane and benzidine.44 Different colored powder precipitates were also obtained for P(oPD), P(4Me-oPD), P(dMe-oPD) and P(tBu-oPD) polymers, depending on the experimental conditions (Table 1). In this study, it was possible to prepare polymers of oPD, 4MeoPD, dMe-oPD and tBu-oPD in high yield, using a mixture of Al(OTf)3
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Using Al(OTf)3 to polymerize o-phenylenediamine

NH2 NH2 NH2 NH2

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NH2 NH2 H3C NH2

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CH3 4,5-dimethyl-o-phenylenediamine (dMe-oPD)

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Figure 1. Aromatic diamine monomer structures used in this study.

Table 1. Reaction conditions for the polymerization of oPD and derivatives using chemical oxidative polymerization with (NH4 )2 S2 O8 as oxidant for 24 h Powder color Dark brown Dark brown Black Brown Dark brown Brown Light brown Brown Light brown Dark brown Brown Dark brown Co-catalyst /solvent H2 O HCl/H2 O Al(OTf)3 /H2 O H2 O HCl/H2 O Al(OTf)3 /H2 O H2 O HCl/H2 O Al(OTf)3 /H2 O H2 O HCl/H2 O Al(OTf)3 /H2 O T a ( C) 100 30 100 100 30 100 100 30 100 100 30 100 Yield (wt%) 90.0 53.0 85.0 82.0 77.0 83.0 72.0 67.0 75.0 63.0 61.0 73.0

Table 2. Solubility data of the polymers in different solvents (at room temperature) Run Polymer P(oPD) P(oPD) P(oPD) P(4Me-oPD) P(4Me-oPD) P(4Me-oPD) P(dMe-oPD) P(dMe-oPD) P(dMe-oPD) P(tBu-oPD) P(tBu-oPD) P(tBu-oPD) NMP 93 89 96 100 100 100 100 100 100 100 100 100 DMSO 89 91 92 100 96 100 100 100 100 100 100 100 DMF 79 84 93 100 89 100 100 100 100 100 100 100 H2 SO4 100 92 100 100 100 100 100 100 100 100 100 100 THF 37 25 44 79 73 83 74 86 87 90 92 91 CHCl3 35 31 42 81 65 85 81 78 84 87 88 89

Run 1 2 3 4 5 6 7 8 9 10 11 12
a

Polymer P(oPD) P(oPD) P(oPD) P(4Me-oPD) P(4Me-oPD) P(4Me-oPD) P(dMe-oPD) P(dMe-oPD) P(dMe-oPD) P(tBu-oPD) P(tBu-oPD) P(tBu-oPD)

1 2 3 4 5 6 7 8 9 10 11 12

Reaction temperature.

and ammonium persulfate as oxidant in water (Table 1). Black and brown polymer powders were obtained with polymerization yields of 85%, 83%, 75% and 73%, respectively. The high yield obtained using Al(OTf)3 as a co-catalyst is probably due to the fact that Al(OTf)3 does not form monomer salts which lower the polymerization yield, as is the case with the use of protic acids.48,49 Solubility of polymers It has been reported that the solubility of aromatic diamine polymers depends mainly on their macromolecular structures and the composition of the solution used for the polymerization.2 The solubility was measured by adding 10 mL of the solvent to 100 mg of polymer sample and dispersing thoroughly. After the mixture was stirred continuously for several hours at room temperature, the solubility was characterized quantitatively for all solvents. Table 2 shows the effect of polymerization conditions on the solubility of P(oPD), P(4Me-oPD), P(dMe-oPD) and P(tBu-oPD) polymers in different solvents. Generally, all P(oPD), P(4Me-oPD), P(dMe-oPD) and P(tBu-oPD) polymers can be considered as soluble in N-methylpyrrolidone (NMP), DMSO, dimethylformamide (DMF) and sulfuric acid (H2 SO4 ) solvents, which are considered to be good solvents of polyaniline polymers,2,20,40 as shown in Table 2. In addition, P(4Me-oPD), P(dMe-oPD) and P(tBu-oPD) polymers were mainly soluble in tetrahydrofuran (THF) and chloroform (CHCl3 ) solvents while P(oPD) polymers were partly soluble in the THF and CHCl3 solvents (Table 2). It can be concluded from these results that the solubility of P(oPD) polymers was improved by
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introducing side substituents in the polymer chain. The side groups allow greater distortions of the polymer chains and decrease the interchain van der Waals force owing to steric hindrance, which improves the solubility. Furthermore, side groups in the polymer chains lead to more solvation sites, which can also increase the solubility.20 Correspondingly, Tsuchida et al. suggested that the solubility is mainly determined by molecular structure rather than molecular weight of the polymers as long as the molecular weight is not too low.51 However, the solubility of polymers was almost independent of the reaction time of polymer synthesis.52 FTIR spectroscopy In the FTIR spectra of P(oPD), P(4Me-oPD), P(dMe-oPD) and P(tBu-oPD) polymers (Figs 2(A) 2(D)) all polymers exhibited two or three broad bands at 34003200 and 31503100 cm1 , suggesting NH stretching vibrations of NH and NH2 groups, respectively.23,38 40,53 Two weak broad peaks at 2970 and 2880 cm1 formed in the P(4Me-oPD) and P(dMe-oPD) spectra (Figs 2(B) and 2(C)) are possibly due to aliphatic CH stretching vibrations of the methyl groups.20,40,54 Both peaks become stronger and bigger in the case of P(tBu-oPD) (Fig. 2(D)) due to the increase of methyl group content in the tert-butyl groups present in the P(tBu-oPD) polymers. In the region between 1580 and 1650 cm1 , as well as between 1400 and 1550 cm1 , the polymers showed strong peaks associated with aromatic ring stretching. Generally, the peak at 16001620 cm1 was attributed to quinonoid rings, whereas the peak at 14701510 cm1 was assigned to benzenoid rings.53 The peaks at 16001620 cm1 exhibit different peak areas compared with the peaks at 14701510 cm1 suggesting that the contents of quinonoid and benzenoid units in the polymers are dissimilar, leading to different polymer ladder structures.2,55

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Figure 2. FTIR spectra of (A) P(oPD), (B) P(4Me-oPD), (C) P(dMe-oPD) and (D) P(tBu-oPD) prepared by chemical oxidative polymerization.

The peaks at 1020820, 710760 and 570590 cm1 were assigned to out-of-plane bending motions of CH of the 1,2,4,5tetrasubstituted benzene nuclei of phenazine units, implying that the polymers have the basic phenazine skeleton. Moreover, the peaks centered at 13301370 and 12101240 cm1 were due to the CN stretching vibration in quinonoid imine units and to CN stretching in the benzenoid unit respectively.2,40 It can be concluded that the oxidative polymerization of P(oPD), P(4MeoPD), P(dMe-oPD) and P(tBu-oPD) polymers led to relatively small differences in the FTIR spectra of the nal polymers, as was also found in a study by Li et al.2 The FTIR spectra of P(oPD), P(4Me-oPD), P(dMe-oPD) and P(tBu-oPD) polymers suggest that these polymers have a 1,4-substituted benzenoid-quinonoid backbone structure, containing one NH2 group on each 1,4-substituted benzenoid or quinonoid unit.23 NMR spectroscopy H NMR of the polymers The 1 H NMR spectra of the P(tBu-oPD), P(dMe-oPD), P(4Me-oPD) and P(oPD) polymers are shown in Fig. 3, curves (a), (b), (c)
1

and (d) respectively. The 1 H NMR spectra of the P(oPD), P(4MeoPD), P(dMe-oPD) and P(tBu-oPD) polymers in deuterated DMSO obtained in water using ammonium persulfate as an oxidant are characterized by three sharp peaks at 7.0, 7.1 and 7.2 ppm, which correspond to NH2 and NH protons on the phenazine unit, as shown in Fig. 3. Also another peak centered at 6.5 ppm (Fig. 3, curve (b)) is possibly due to NH protons in P(dMe-oPD) polymers.40 The broad peaks centered at 8.0, 8.2, 9.5 and 9.8 ppm are attributed to the aromatic protons on the phenazine unit, and correlate well with results obtained in previous studies.2,23,35,36,39,53 In addition, peaks located in the range from 1.0 to 2.2 ppm are assigned to methyl group protons on the benzenoid units (Fig. 3, curves (a), (b) and (c)). These methyl protons become stronger in the case of the P(tBu-oPD) spectrum (Fig. 3(a)) due to an increase in methyl group content in the P(tBu-oPD) polymers. Two additional strong peaks at 2.5 and 3.4 ppm are due to DMSO protons and water in DMSO. In general, it appears that the differences in the chemical shifts and intensities in the 1 H NMR spectra of P(oPD), P(4Me-oPD), P(dMe-oPD) and P(tBu-oPD) polymers could result from different molecular structures and molecular weights.48
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Using Al(OTf)3 to polymerize o-phenylenediamine

c NH2 N N CH3 b CH3 b a

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Figure 4. 13 C NMR spectra of P(4Me-oPD) (curve (a)), P(dMe-oPD) (curve (b)) and P(tBu-oPD) (curve (c)) prepared by chemical oxidative polymerization with ammonium persulfate in water using deuterated DMSO at 600.17 MHz.

Figure 3. 1 H NMR spectra of P(tBu-oPD) (curve (a)), P(dMe-oPD) (curve (b)), P(4Me-oPD) (curve (c)) and P(oPD) (curve (d)) prepared by chemical oxidative polymerization with ammonium persulfate in water using deuterated DMSO at 600.17 MHz.

C NMR of the polymers The 13 C NMR spectra of the P(4Me-oPD), P(dMe-oPD) and P(tBuoPD) polymers are shown in Fig. 4, curves (a), (b) and (c) respectively. The peaks centered at 116129 ppm are assigned to the hydrogen-bonded carbon (CH) in the benzenoid unit and the peaks at 138142 ppm are attributed to the nitrogen-bonded carbon (CNH) in the benzenoid unit.39,54,56 58 The peaks at 151156 ppm (Fig. 4, curve (c)) are possibly due to C=N in the quinonoid unit.39,58 Furthermore, other peaks centered at 1822 ppm (Fig. 4, curves (a) and (b)) are due to the methyl groups on the benzenoid units, while the methyl group peaks in tert-butyl units appear at 3034 ppm as can be seen in Fig. 4, curve (c). These results are comparable with results obtained by Sestrem et al. for oligomers of oPD.53 WAXD of the polymers Wide-angle X-ray diffractograms of the P(oPD), P(4Me-oPD), P(dMe-oPD) and P(tBu-oPD) polymers are shown in Figs 5(A),5(B), 5(C) and 5(D), respectively. P(oPD) polymers (Fig. 5(A)) seemed to show the strongest diffraction intensity at 2 7 and two medium broad peaks positioned at 2 = 17 and 25 , which are attributed to diffraction by an amorphous polymer.39,48 P(4Me-oPD) polymers prepared in HCl solution (Fig. 5(B), curve (b)) and Al(OTf)3 solution (Fig. 5(A), curve (c)) show strong diffraction intensity at 2 7 as well as two medium broad peaks at 2 = 14 and 25 . Only one medium broad peak at 2 = 25 was observed for P(4MeoPD) polymer prepared in water (Fig. 5(A), curve (a)), attributed to the diffraction of an amorphous polymer. Note that the peak at 2 = 25 for P(oPD) polymers (Fig. 5(A)) is stronger than that for P(4Me-oPD) polymers (Fig. 5(B)). This indicates that the supermolecular structure of the P(oPD) polymers is different from that of the P(4Me-oPD) polymers. Moreover, P(tBu-oPD) polymers
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prepared in water (Fig. 5(D), curve (a)) and HCl solution (Fig. 5(D), curve (b)) show a medium broad peak at 2 = 17 , while P(tBu-oPD) polymer prepared in Al(OTf)3 solution (Fig. 5(A),curve (c)) shows three peaks at 2 = 9 , 17 and 25 . In contrast, the XRD patterns of P(dMe-oPD) polymers (Fig. 5(C)) show a series of sharp peaks in the region of 10 < 2 < 50 , and there is small broad reection due to amorphous components, which indicates that P(dMe-oPD) polymers are polycrystalline in nature and have better crystallinity than P(tBu-oPD) polymers, which could be due to the steric hindrance of the large tertbutyl groups on the P(tBu-oPD) polymers that disturb polymer chain ordering. This leads to an increase in the spacing and randomness of intermolecular and intramolecular chains as well as the amorphous nature of the polymers.54 UVvisible spectra of the polymers Figure 6, curves (a), (b), (c) and (d), shows the UV visible spectra of the P(oPD), P(4Me-oPD), P(dMe-oPD) and P(tBu-oPD) polymers, respectively. They display two strong absorption bands at 260280 and 370 430 nm. The absorption bands between 370 and 430 nm are ascribed to * transitions in the phenazine ring conjugated to the two lone pairs of nitrogen of the NH2 groups (phenazine has an absorbance at 364 nm). The absorption bands in the range 260 280 nm are due to * transitions of the benzenoid and quinonoid structures.35,39,40,59 62 However, two small additional absorption bands at 590 and 640 nm in the P(tBu-oPD) polymer (Fig. 6, curve (d)) were observed, which can be attributed to quinonediimine-like units (similar to those observed in the emeraldine form of polyaniline) in the polymer chain.40,63,64 Moreover, the intensity ratios and wavelengths of the absorption bands of the different polymers in Fig. 6 differed to some extent.

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Figure 5. WAXD of (A) P(oPD), (B) P(4Me-oPD), (C) P(dMe-oPD) and (D) P(tBu-oPD) prepared by chemical oxidative polymerization.

(a) P(oPD)/[H2O] (b) P(4Me-oPD)/[H2O] (c) P(dMe-oPD)/[H2O] (d) P(tBu-oPD)/[H2O]

This may be attributed to the different oxidative degrees and quinonoid contents in the polymer structures.40 Electrical conductivity The bulk electrical conductivity of the polymers was measured by a two-disk method using a UT 70A multimeter at ambient temperature. Most of the polymers exhibited conductivity less than 1 108 S cm1 . Unfortunately, it was not possible to evaluate the effect of the methyl and tert-butyl side groups on the electrical conductivity of these polymers. The low electrical conductivity of phenylenediamine polymers can be attributed to the bulky NH2 substituents which cause main-chain twisting, leading to a reduction in its coplanarity, resulting in a barrier to the intrachain transfer and interchain jumping of the electrons and thereby shortening the conjugation length.2,4,10,65,66 It was reported by Goyette and Leclerc that the presence of bulky substituents adversely affects the interchain electrical transport which leads to poor electrical conductivity.67 On the other hand, copolymerization of phenylenediamines with other comonomers, which have different functional groups, may possibly improve the electrical conductivity of these polymers.2,4,10,65,66
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Figure 6. UVvisible absorption spectra in DMSO of P(oPD) (curve (a)), P(4Me-oPD) (curve (b)), P(dMe-oPD) (curve (c)) and P(tBu-oPD) (curve (d)) prepared by chemical oxidative polymerization.

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Table 3. DSC thermal data of the polymer powders Glass temperature T g ( C) 261271 267275 266273 271274 Crystallization temperature T c ( C) 403429 414427 422429 Melting temperature T m ( C) 408432 420434 424433 Heat of crystallization Hc (J g1 ) 10.225.1 15.826.0 12.025.7 Heat of fusion Hm (J g1 ) 11.325.4 19.247.7 20.132.0

Polymer P(oPD) P(4Me-oPD) P(dMe-oPD) P(tBu-oPD)

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Cooling profile Exo T g

(B) 0.4 0.0 Heat Flow (W/g) -0.4 -0.8 -1.2 -1.6 -2.0

P(4Me-oPD)/[Al(OTf)3]
(a) Cooling profile Exo

Heat Flow (W/g)

-1.6 -2.4 -3.2 -4.0 -4.8 -5.6 100 150 200

(b) Second heating profile

Endo

Endo

250 300 350 Temperature (C)

400

450

500

-2.4 100

150

200

250 300 350 Temperature (C)

400

450

500

(C) 0.4 0.0 Heat Flow (W/g)

P(dMe-oPD)/[Al(OTf)3]
Exo

(D) 0.0
-0.4

P(tBu-oPD)/[Al(TOf)3]
Exo (a) Cooling profile

Heat Flow (W/g)

-0.4 (a) Cooling profile -0.8 -1.2

(b) Second heating profile

-0.8 -1.2 -1.6 -2.0 -2.4 100

(b) Second heating profile Endo

-1.6 -2.0 -2.4 -2.8 100 150 200 250 300 350 Temperature (C) 400 450 500
Endo

150

200

250 300 350 Temperature (C)

400

450

500

Figure 7. DSC scans of (A) P(oPD), (B) P(4Me-oPD), (C) P(dMe-oPD) and (D) P(tBu-oPD) prepared by chemical oxidative polymerization.

Thermal analysis of polymers DSC of the polymers Table 3 and Fig. 7 represent the thermal data and DSC scans of the P(oPD), P(4Me-oPD), P(dMe-oPD) and P(tBu-oPD) polymers. It can be seen that all polymers exhibited glass transition temperatures T g in the range 261275 C. The glass transition temperatures were taken as the midpoints of the change in slope of the baselines in DSC cooling curves (Fig. 7(A)). The high glass transition temperatures of these polymers are probably due to the high rigidity of the polymer chains.68 However, DSC detected no melting transitions of P(oPD) polymers, although it was possible to detect crystallization and melting temperatures for most P(4Me-oPD), P(dMe-oPD) and P(tBu-oPD) polymers ranging from 403429 C and 408434 C respectively. Generally, P(dMe-oPD) polymers showed higher heats of crystallization and melting than P(tBu-oPD) and P(4Me-oPD) polymers, while P(4Me-oPD) polymers exhibited the lowest heats of crystallization and melting, as can be seen in Table 3. This means that P(dMe-oPD) polymers have higher crystalline structures than P(tBu-oPD) and P(4Me-oPD) polymers. This corresponds to the results obtained by WAXD. The DSC results also showed that
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P(4Me-oPD), P(dMe-oPD) and P(tBu-oPD) polymers have excellent thermal stability (no decomposition up to 400 C) and this would make them useful for utilization by the engineering industry and also make them easier to process.69 TGA of the polymers Figure 8 shows the TGA curves of polymer powders of P(oPD), P(4Me-oPD), P(dMe-oPD) and P(tBu-oPD) in owing nitrogen. The polymers exhibit two weight loss processes. The rst weight loss of 6%8% at 80100 C is probably due to evaporation of water molecules trapped in the polymer chains. The second weight loss starting at about 220400 C is associated with the thermal degradation of polymer chains. The P(oPD), P(4Me-oPD), P(dMeoPD) and P(tBu-oPD) polymers revealed different thermal behavior due to their difference in molecular structure. In general, P(4MeoPD) polymers showed higher thermal stability than the other polymers (Fig 8). The polymers showed an initial decomposition temperature (T 0 ) and a temperature for 10% weight loss (T 10 ) in the range 180280 C and 260380 C, respectively. Moreover, the char yields of the polymers at 600 C were about 40%70%. These

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(A) 110 100 90 Weight (%) 80 70 60 50 40 30 20 100 200 300 400 500 600 700 800 900 Temperature (C) (C) 110 100 90 Weight (%) Weight (%) 80 70 60 50 40 30 100 200 300 400 500 600 700 800 900 Temperature (C)
P(dMe-oPD)/[H2O] P(dMe-oPD)/[HCl] P(dMe-oPD)/[Al(OTf)3]

I Amer, DA Young, HCM Vosloo

(B) 110
100 90
P(4Me-oPD)/[H2O] P(4Me-oPD)/[HCl] P(4Me-oPD)/[Al(OTf)3]

P(oPD)/[H2O] P(oPD)/[HCl] P(oPD)/[Al(OTf)3]

Weight (%)

80 70 60 50 40 30

100

200

300

400

500

600

700

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900

Temperature (C) (D) 110 100 90 80 70 60 50 40 30 100 200 300 400 500 600 700 800 900 Temperature (C)
P(tBu-oPD)/[H2O] P(tBu-oPD)/[HCl] P(tBu-oPD)/[Al(OTf)3]

Figure 8. TGA curves of the polymer powders of (A) P(oPD), (B) P(4Me-oPD), (C) P(dMe-oPD) and (D) P(tBu-oPD) in nitrogen at a heating rate of 10 C min1 .

Table 4. TGA thermal data of the polymer powders T0 ( C) 210220 230280 210215 180220 T 10 ( C) 320380 310380 260280 260360 T max a ( C) 510580 530590 460550 500550 Char yield at 600 C (%) 4370 6062 4456 4055

Polymer P(oPD) P(4Me-oPD) P(dMe-oPD) P(tBu-oPD)

a

Maximum decomposition temperature.

results are comparable with the results obtained for polyaniline which make them interesting polymers.70,71 Table 4 summarizes the TGA results obtained for the P(oPD), P(4Me-oPD), P(dMe-oPD) and P(tBu-oPD) polymers. These polymers show good thermal stability and heat resistance due to their rigid chain structure.

with P(oPD) polymers, suggesting that the solubility of the P(oPD) polymers can be improved by introducing side groups on the benzenoid rings. FTIR, UVvisible, 1 H NMR and 13 C NMR spectra of the P(4Me-oPD), P(dMe-oPD) and P(tBu-oPD) polymers displayed relatively small differences between them but showed that these polymers consist of aminophenazine units containing both quinonoid and benzenoid structures. The WAXD measurements indicated that most polymers are generally amorphous except P(dMe-oPD) polymers which showed some crystalline structure. On the other hand, DSC results showed that P(4Me-oPD), P(dMeoPD) and P(tBu-oPD) polymers have crystalline structures but P(oPD) polymers do not show any crystalline structure, which can be explained by the methyl and tert-butyl groups situated in positions 4 and 5 on the benzenoid rings of the P(4Me-oPD), P(dMe-oPD) and P(tBu-oPD) polymers limiting the formation of ladder structures and leading to higher content of linear structure polymers. Moreover, the polymers showed good thermal stability, but they showed a different thermal behavior due to their different molecular structure.

CONCLUSIONS
In this work, P(oPD), P(4Me-oPD), P(dMe-oPD) and P(tBu-oPD) polymers were successfully synthesized in high polymerization yield by a chemical oxidative polymerization using ammonium persulfate as the oxidant catalyst and Al(OTf)3 as a co-catalyst. Al(OTf)3 generally leads to improved yield of most polymers. In general, the P(4Me-oPD), P(dMe-oPD) and P(tBu-oPD) polymers exhibited a slightly lower yield but better solubility compared

ACKNOWLEDGEMENTS
The authors wish to thank the North-West University, Potchefstroom, for awarding a research fellowship to I. Amer, SASOL (South Africa) for nancial support, the South African Department of Science and Technology, THRIP Project, for funding (TP 2010072200011), Dr Dawie Joubert and Dr Jonathan Mole
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Using Al(OTf)3 to polymerize o-phenylenediamine from SASOL for TGA measurements and Mr Andre Joubert for NMR measurements.

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